基于Janus乳液的新型燃油脱硫体系的构建

发布时间：2018-03-01 13:12

  本文关键词： 脱硫 乳化 Janus纳米片 破乳 循环利用　出处：《辽宁大学》2017年硕士论文　论文类型：学位论文

【摘要】：Janus乳化是基于其功能性分区的表面对两相不互溶体系同时具有相亲性而形成的乳化现象。与微乳化不同之处在于Janus乳化剂多为固态的Janus材料,其不仅可以实现两相不互溶体系的有效乳化,而且通过简单的操作,如离心,即可实现破乳,乳化剂亦可重复使用。本文成功合成出一系列兼具乳化剂和催化剂双重功能的离子液体基Janus纳米片,并首次将其应用于燃油氧化脱硫体系,实现了模型油的深度氧化脱硫。离子液体基Janus纳米片的制备,首先采用Pickering乳液界面材料化法,以三种硅烷化试剂为前驱体得到一侧为亲水基团的咪唑啉基,而另外一侧为亲油的苯基修饰的Janus石蜡球。利用四氢呋喃对石蜡良好的溶解性将石蜡内核溶解后得到Janus中空球,进一步通过细胞超声粉碎机粉碎,最终得到了咪唑啉基Janus纳米片。其次,通过氯代正丁烷与Janus片上咪唑啉基之间的离子交换反应,制备了阴离子为Cl-的离子液体基Janus纳米片。最后,利用离子交换反应,将[HSO4]-、[SiW12O40]4-、[PMo12O40]3-以及[PW12O40]3-引入到离子液体基Janus纳米片上,从而得到了一种兼具催化剂和乳化剂双功能的新型离子液体基Janus纳米片。通过SEM、EDS、FT-IR以及XPS对其进行表征,结果表明四种酸根离子被成功固载到离子液体基Janus纳米片上。分别以四种离子液体基Janus纳米片为固体乳化剂对离子液体[BMIM]BF4和正辛烷进行乳化性能分析。结果显示四种离子液体基Janus纳米片均能将离子液体[BMIM]BF4和正辛烷乳化,并形成稳定的乳液体系。通过光学电子显微镜可明显观察到乳液液滴的存在。本文首次将四种离子液体基Janus纳米片应用于燃油氧化脱硫体系,并实现了模型油的深度氧化脱硫。结果表明:[BMIM]3PMo12O40基Janus纳米片为脱硫体系最佳催化剂。实验确定了最佳反应条件:催化剂用量为30 mg,O/S=5,T=50℃。在此基础上考查了[BMIM]3PMo12O40基Janus纳米片的脱硫性能。结果表明:当反应进行到1.5小时,二苯并噻吩(DBT)脱硫率达到100%,且进行六次循环利用,DBT的脱硫率依然能达到99.8%,无明显下降。
[Abstract]:The emulsification of Janus is based on the fact that the surface of its functional partition is compatible with the two-phase immiscible system, which is different from microemulsification in that the Janus emulsifiers are mostly solid-state Janus materials. It can not only realize the effective emulsification of two-phase insoluble system, but also realize demulsification by simple operation, such as centrifugation. In this paper, a series of ionic liquid-based Janus nanoparticles with dual functions of emulsifier and catalyst have been successfully synthesized and applied to the fuel oil oxidation desulfurization system for the first time. Deep oxidation desulfurization of model oil was realized. Imidazoline group with hydrophilic group on one side was obtained by Pickering emulsion interfacial material method. On the other side, the oil-friendly phenyl modified Janus paraffin spheres were obtained by using the good solubility of tetrahydrofuran to dissolve the paraffin core to obtain the Janus hollow spheres, which were further crushed by a cellular ultrasonic pulverizer. Finally, Imidazolinyl Janus nanoparticles were obtained. Secondly, ionic liquid-based Janus nanoparticles with anions as Cl- were prepared by ion exchange reaction between chloro-n-butane and Imidazoline groups on Janus tablets. Finally, ion exchange reaction was used. [HSO4] -, [SiW12O40] 4, [PMo12O40] 3- and [PW12O40] 3- were introduced into ionic liquid-based Janus nanoparticles, and a novel ionic liquid-based Janus nanochip with dual functions of catalyst and emulsifier was obtained, which was characterized by SEM-EDSFT-IR and XPS. The results showed that four kinds of acid ions were successfully immobilized on the ionic liquid-based Janus nanoparticles, and the emulsifying properties of the ionic liquids [BMIM] BF4 and n-octane were analyzed using four kinds of ionic liquid-based Janus nanoparticles as solid emulsifiers respectively. The results showed that the emulsifying properties of the ionic liquids [BMIM] BF4 and n-octane were analyzed. Four kinds of ionic liquid-based Janus nanoparticles can emulsify the ionic liquid [BMIM] BF4 and n-octane. The existence of emulsion droplets can be observed by optical electron microscope. In this paper, four kinds of ionic liquid-based Janus nanoparticles were first used in the fuel oil oxidative desulfurization system. The results show that [BMIM] 3PMo12O40-based Janus nanoparticles are the best catalyst for desulfurization system. The optimum reaction conditions are determined as follows: the amount of catalyst is 30 mg / O / S ~ (5) T ~ (+) ~ (50 鈩，

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